Curable composition and method for producing the same

ABSTRACT

Disclosed herein is a curable composition excellent in workability, adhesion properties, rubber-like properties, storage stability, and quick curability. The curable composition comprises (A) a crosslinkable silyl group-containing organic polymer and (B) a (meth)acrylic polymer obtained by polymerizing a (meth)acrylic monomer having a polymerizable unsaturated bond in the presence of a metallocene compound and a crosslinkable silyl group-containing thiol compound, at least one end of the (meth)acrylic polymer being bonded to a residue, —S—R 3  (where R 3  represents a group having a crosslinkable silyl group) obtained by removing a hydrogen atom from the crosslinkable silyl group-containing thiol compound.

TECHNICAL FIELD

The present invention relates to a curable composition, moreparticularly to a curable composition excellent in adhesion properties,rubber-like properties, quick curability, and production stability.

BACKGROUND ART

An acrylic polymer obtained by polymerization using a specialpolymerization catalyst is disclosed in Patent Document 1. PatentDocument 1 also discloses a curable composition composed of such aspecial acrylic polymer and a silane coupling agent. However, thecurable composition is still poor in, for example, adhesion propertiesand rubber-like properties.

On the other hand, room temperature-curable compositions containingcrosslinkable silyl group-containing organic polymers have already beenindustrially produced, and have been widely used for sealants,adhesives, coating materials, and the like. In general, these curablecompositions contain various metal catalysts so as to have curability.The kind of metal catalyst to be used and the amount thereof to be addedare varied depending on the purpose of use of the curable compositions.

As such catalysts, reaction products of organotin compounds with estercompounds have been conventionally known (see, for example, PatentDocuments 2-5). Particularly, catalysts obtained by using phthalateesters as the ester compounds have been generally used. However, thephthalate esters are volatile organic compounds (VOC) whose guidelinevalues have been specified by Ministry of Health, Labor and Welfare, andthe use of the phthalate esters is being perceived as a problem. Inrecent years, it is therefore desired that catalysts be designed withoutusing the phthalate esters.

Meanwhile, there have been high market demands for quickly-curableproducts, but such quickly-curable products have a disadvantage thatthey are cured in course of production. For example, Patent Document 5discloses an organic polymer containing a crosslinkable silyl grouprepresented by —SiX₃ and a curable composition containing a reactionproduct of dialkyltinoxide with an ester-based compound. However, such acurable composition has caused a problem that products are cured incourse of production due to its high reactivity. In a case where anorganotin compound-based curing catalyst having a relatively lowreactivity is used in view of production stability, quick curabilitycannot be attained. On the other hand, in a case where an organotincompound-based curing catalyst having a relatively high reactivity isused in view of quick curability, production stability cannot beattained as is the case with the product containing a reaction productof dialkyltinoxide with an ester-based compound.

Recently, equipment which can produce catalysts in a completely enclosedsystem has been developed, and is being well received by manufacturersof room temperature-curable products. However, introduction of suchequipment involves some problems that there is a limit to the number ofadditives and the equipment is very expensive. Under the circumstances,the present inventors have intensively investigated an organotincompound-based curing catalyst which can exhibit high activity after acertain length of time has elapsed, which has led to the completion ofthe present invention.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-40037

Patent Document 2: Examined Japanese Patent Application Publication No.1-58219

Patent Document 3: Japanese Patent No. 3062625

Patent Document 4: Japanese Patent Application Laid-Open No. 8-337713

Patent Document 5: Japanese Patent Application Laid-Open No. 2003-138151

Patent Document 6: Japanese Patent Application Laid-Open No. 11-12480

Patent Document 7: Japanese Patent Application Laid-Open No. 52-73998

Patent Document 8: Japanese Patent Application Laid-Open No. 55-9669

Patent Document 9: Japanese Patent Application Laid-Open No. 59-122541

Patent Document 10: Japanese Patent Application Laid-Open No. 60-6747

Patent Document 11: Japanese Patent Application Laid-Open No. 61-233043

Patent Document 12: Japanese Patent Application Laid-Open No. 63-112642

Patent Document 13: Japanese Patent Application Laid-Open No. 3-79627

Patent Document 14: Japanese Patent Application Laid-Open No. 4-283259

Patent Document 15: Japanese Patent Application Laid-Open No. 5-70531

Patent Document 16: Japanese Patent Application Laid-Open No. 5-287186

Patent Document 17: Japanese Patent Application Laid-Open No. 11-80571

Patent Document 18: Japanese Patent Application Laid-Open No. 11-116763

Patent Document 19: Japanese Patent Application Laid-Open No. 11-130931

Patent Document 20: Japanese Patent No. 3313360

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

In view of the problems associated with prior art, it is one object ofthe present invention to provide a curable composition excellent inworkability, adhesion properties, rubber-like properties, and storagestability. Further, it is another object of the present invention toprovide a curable composition excellent in quick curability, productionstability, product stability, and adhesion properties without using aphthalate ester.

Means for Solving the Problems

In order to solve the above problems, a first aspect of the presentinvention is directed to a curable composition including:

(A) a crosslinkable silyl group-containing organic polymer; and

(B) a (meth)acrylic polymer obtained by polymerizing a (meth)acrylicmonomer having a polymerizable unsaturated bond in the presence of ametallocene compound represented by the following formula (1) and acrosslinkable silyl group-containing thiol compound, at least one end ofthe (meth)acrylic polymer being bonded to a residue, —S—R³ (where R³represents a group having a crosslinkable silyl group) obtained byremoving a hydrogen atom from the crosslinkable silyl group-containingthiol compound. It is to be noted that in this specification, the term“(meth)acrylic” includes both acrylic and methacrylic.

[Formula 1]

(where M represents a metal selected from the group consisting of metalsof Groups 4, 5, and 14 of the periodic table, chromium, ruthenium, andpalladium; R¹ and R² each independently represent at least one groupselected from the group consisting of substituted or unsubstitutedaliphatic hydrocarbon groups, substituted or unsubstituted alicyclichydrocarbon groups, substituted or unsubstituted aromatic hydrocarbongroups, and substituted or unsubstituted silicon-containing groups, ahydrogen atom or a single bond, provided that R¹ and R² may cooperatewith each other to bond the two five-membered rings of the compoundrepresented by the formula (1) and provided that the plurality ofadjacent groups R¹ or R² may cooperate with each other to form a cyclicstructure; a and b each independently represent an integer of 1 to 4; Yrepresents a halogen atom or a hydrocarbon group in which at least partof hydrogen atoms may be substituted with a halogen atom; and n is 0 oran integer obtained by subtracting 2 from the valence of the metal M.)

In the present invention, it is preferred that the main chain of the(meth)acrylic polymer (B) contain a repeating unit represented by thefollowing formula (2) in an amount of 99% by weight or less, and furthercontain as a repeating unit other than the repeating unit represented bythe formula (2), a repeating unit derived from a polymerizableunsaturated compound monomer having one or more crosslinkable silylgroups in the molecule, in an amount of 1 to 50% by weight:

[Formula 2]

(where R⁴ to R⁶ each independently represent a hydrogen atom, a halogenatom or an alkyl group having 1 to 3 carbon atoms, and R⁷ represents ahydrogen atom, an alkali metal atom or a hydrocarbon group having 1 to22 carbon atoms (the hydrocarbon group may be linear or may have a sidechain; at least part of hydrogen atoms of the hydrocarbon group or of agroup constituting the side chain of the hydrocarbon group may besubstituted with at least one polar group or reactive functional groupselected from the group consisting of a chlorine atom, a fluorine atom,a primary amino group, a secondary amino group, a tertiary amino group,a quaternary amine salt group, an amido group, an isocyanate group, analkylene oxide group, a hydroxysilyl group, a methoxysilyl group, anethoxysilyl group, a propoxysilyl group, a chlorosilyl group, aburomosilyl group, and a glycidyl group; the hydrocarbon group may havea double bond; and the hydrocarbon group may have a cyclic structure).)

Further, it is also preferred that the crosslinkable silyl group of the(meth)acrylic polymer (B) be represented by the following generalformula (3):

[Formula 3]—Si X₃  (3)

(where X represents a hydroxyl or hydrolyzable group and three Xs may bethe same or different.)

Furthermore, it is also preferred that the (meth)acrylic polymer (B)contain both of a crosslinkable silyl group represented by the followinggeneral formula (3) and a crosslinkable silyl group represented by thefollowing general formula (4):

[Formula 3]—Si X₃  (3)[Formula 4]

(where X represents a hydroxyl or hydrolyzable group; when the pluralityof Xs exist, they may be the same or different; R⁸ represents asubstituted or unsubstituted monovalent organic group having 1 to 20carbon atoms; when the plurality of R⁸s exist, they may be the same ordifferent; and c is 1 or 2.)

Moreover, it is also preferred that the (meth)acrylic polymer (B) be amixture of a (meth)acrylic polymer containing a crosslinkable silylgroup represented by the following general formula (3) and a(meth)acrylic polymer containing a crosslinkable silyl group representedby the following general formula (4):

[Formula 3]—Si X₃  (3)[Formula 4]

(where X represents a hydroxyl or hydrolyzable group; when the pluralityof Xs exist, they may be the same or different; R⁸ represents asubstituted or unsubstituted monovalent organic group having 1 to 20carbon atoms; when the plurality of R⁸s exist, they may be the same ordifferent; and c is 1 or 2.)

In the first aspect of the present invention, it is preferred that thecurable composition further contains a curing catalyst (C). In thiscase, the curing catalyst (C) preferably contains an organotin compound(C1) represented by the following general formula (5):

[Formula 5]R⁹R¹⁰SnO  (5)

(where R⁹ and R¹⁰ each represent a monovalent hydrocarbon group.)

In the first aspect of the present invention, in a case where thecurable composition contains the organotin compound (C1) as a curingcatalyst, the curable composition containing the components (A), (B) and(C1) is preferably subjected to reaction treatment.

A second aspect of the present invention is directed to a curablecomposition including:

(A) a crosslinkable silyl group-containing organic polymer; and

(C1) an organotin compound represented by the following general formula(5):

[Formula 5]R⁹R¹⁰SnO  (5)

(where R⁹ and R¹⁰ each represent a monovalent hydrocarbon group.)

In the second aspect of the present invention, the curable compositioncontaining the components (A) and (C1) is preferably subjected toreaction treatment.

In the first and second aspects of the present invention, the polymer(A) of the curable composition is preferably an organic polymercontaining a crosslinkable silyl group represented by the followinggeneral formula (3):

[Formula 3]—Si X₃  (3)

(where X represents a hydroxyl or hydrolyzable group and three Xs may bethe same or different.)

In the first and second aspects of the present invention, the polymer(A) of the curable composition is preferably an organic polymercontaining both of a crosslinkable silyl group represented by thefollowing general formula (3) and a crosslinkable silyl grouprepresented by the following general formula (4):

[Formula 3]—Si X₃  (3)[Formula 4]

(where X represents a hydroxyl or hydrolyzable group; when the pluralityof Xs exist, they may be the same or different; R⁸ represents asubstituted or unsubstituted monovalent organic group having 1 to 20carbon atoms; when the plurality of R⁸s exist, they may be the same ordifferent; and c is 1 or 2.

In the first and second aspects of the present invention, the polymer(A) of the curable composition is preferably a mixture of an organicpolymer containing a crosslinkable silyl group represented by thefollowing general formula (3) and an organic polymer containing acrosslinkable silyl group represented by the following general formula(4):

[Formula 3]—Si X₃  (3)[Formula 4]

(where X represents a hydroxyl or hydrolyzable group; when the pluralityof Xs exist, they may be the same or different; R⁸ represents asubstituted or unsubstituted monovalent organic group having 1 to 20carbon atoms; when the plurality of R⁸s exist, they may be the same ordifferent; and c is 1 or 2.)

In the first and second aspects of the present invention, the polymer(A) of the curable composition is preferably at least one selected fromthe group consisting of a crosslinkable silyl group-containingpolyoxyalkylene-based polymer, a crosslinkable silyl group-containing(meth)acrylic-modified polyoxyalkylene-based polymer, a crosslinkablesilyl group-containing polyisobutylene-based polymer, and acrosslinkable silyl group-containing (meth)acrylic polymer.

In the first and second aspects of the present invention, it ispreferred that the curable composition further comprise a silanecoupling agent (D).

The present invention is also directed to a method for producing acurable composition including at least the polymer (A) and the organotincompound (C1), the method including subjecting the curable compositionpacked in a hermetically sealed container to reaction treatment.

Effect of the Invention

According to the present invention, it is possible to provide a curablecomposition excellent in workability, adhesion properties, rubber-likeproperties, storage stability, deep-part curability, and quickcurability. Further, according to the present invention, it is alsopossible to provide a curable composition which is highly safe becauseno phthalate ester is used, and is excellent in quick curability,production stability, product stability, and adhesion properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph which shows measurement results of the set to touchtime of each of the curable compositions of Example 10 and ComparativeExample 5.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinbelow, embodiments of the present invention will be described, butthese embodiments are illustrative only and it goes without saying thatvarious modifications can be made without departing from the spirit ofthe present invention.

A first aspect of the present invention is directed to a curablecomposition comprising:

(A) a crosslinkable silyl group-containing organic polymer; and

(B) a (meth)acrylic polymer obtained by polymerizing a (meth)acrylicmonomer having a polymerizable unsaturated bond in the presence of ametallocene compound represented by the following formula (1) and acrosslinkable silyl group-containing thiol compound, at least one end ofthe (meth)acrylic polymer being bonded to a residue, —S—R³ (where R³represents a group having a crosslinkable silyl group) obtained byremoving a hydrogen atom from the crosslinkable silyl group-containingthiol compound:

[Formula 1]

(M represents a metal selected from the group consisting of metals ofGroups 4, 5, and 14 of the periodic table, chromium, ruthenium, andpalladium; R¹ and R² each independently represent at least one groupselected from the group consisting of substituted or unsubstitutedaliphatic hydrocarbon groups, substituted or unsubstituted alicyclichydrocarbon groups, substituted or unsubstituted aromatic hydrocarbongroups, and substituted or unsubstituted silicon-containing groups, ahydrogen atom or a single bond, provided that R¹ and R² may cooperatewith each other to bond the two five-membered rings of the compoundrepresented by the formula (1) and provided that the plurality ofadjacent groups R¹ or R² may cooperate with each other to form a cyclicstructure; a and b each independently represent an integer of 1 to 4; Yrepresents a halogen atom or a hydrocarbon group in which at least partof hydrogen atoms may be substituted with a halogen atom; and n is 0 oran integer obtained by subtracting 2 from the valence of the metal M.)

As the component (A) described above, an organic polymer containing asilicon-containing group which has a hydroxyl or hydrolyzable groupbonded to a silicon atom and can be crosslinked by forming a siloxanebond, that is, an organic polymer containing a crosslinkable silyl groupcan be used. Examples of such a crosslinkable silyl group-containingorganic polymer (A) include those disclosed in Patent Documents 2-20.Specific examples of the crosslinkable silyl group-containing organicpolymer (A) include polyoxyalkylene-based, vinyl-modifiedpolyoxyalkylene-based, (meth)acrylic-modified polyoxyalkylene-based,vinyl-based, polyester-based, and (meth)acrylic ester polymers whichcontain one or more crosslinkable silyl groups in the molecule and maycontain organosiloxane in the main chain, copolymers thereof, andmixtures thereof.

The number of crosslinkable silyl groups is not particularly limited,but one to six crosslinkable silyl groups are generally contained in themolecule from the viewpoint of curing properties of a resultant curablecomposition and physical properties of the cured curable composition.From the viewpoint of ease of crosslinking and ease of production, acrosslinkable silyl group represented by the following general formula(6) is preferably used:

[Formula 6]

(where R⁸ represents a substituted or unsubstituted monovalent organicgroup having 1 to 20 carbon atoms, preferably an alkyl group having 1 to20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkylgroup having 7 to 20 carbon atoms, most preferably a methyl group; whenthe plurality of R⁸s exist, they may be the same or different; Xrepresents a hydroxyl or hydrolyzable group, preferably a group selectedfrom the group consisting of a halogen atom, a hydrogen atom, a hydroxylgroup, an alkoxy group, an acyloxy group, a ketoxymate group, an amidogroup, an acid amide group, a mercapto group, an alkenyloxy group, andan aminooxy group, more preferably an alkoxy group, most preferably amethoxy group; when the plurality of Xs exist, they may be the same ordifferent; and d is 1, 2 or 3, most preferably 3 from the viewpoint ofquick curability.)

In a case where the crosslinkable silyl group-containing organiccompound (A) contains a plurality of crosslinkable silyl groups, thecrosslinkable silyl groups may be the same or different, and the valuesof “d” of the crosslinkable silyl groups represented by the formula (6)may be the same or different. For example, an organic polymer containinga crosslinkable silyl group represented by the following formula (3) anda crosslinkable silyl group represented by the following formula (4) canbe used. Further, a mixture of an organic polymer containing acrosslinkable silyl group represented by the following formula (3) andan organic polymer containing a crosslinkable silyl group represented bythe following formula (4) can also be preferably used.

[Formula 3]—Si X₃  (3)[Formula 4]

(X and R⁸ are the same as those described above with reference to theformula (6), and c is 1 or 2.)

From the viewpoint of physical properties of the cured curablecomposition, such as tensile adhesion properties and modulus, the mainchain of the crosslinkable silyl group-containing organic polymer (A) ispreferably a polyoxyalkylene-based polymer, a (meth)acrylic-modifiedpolyoxyalkylene polymer, a polyisobutylene-based polymer, a(meth)acrylic polymer or a copolymer thereof, and may containorganosiloxane.

Particularly, the crosslinkable silyl group-containing organic polymeris preferably at least one polymer selected from crosslinkable silylgroup-containing polyoxyalkylene-based polymers and crosslinkable silylgroup-containing (meth)acrylic-modified polyoxyalkylene-based polymers.The number average molecular weight of the crosslinkable silylgroup-containing organic polymer (A) is in the range of 1,000 to100,000, preferably in the range of 3,000 to 50,000. The molecularweight distribution is preferably narrow because the uncured curablecomposition is easy to handle due to its low viscosity and the curedcurable composition can have desirable physical properties such asstrength, elongation, and modulus. The crosslinkable silylgroup-containing organic polymers (A) can be used singly or incombination of two or more of them.

As the compound (B), a (meth)acrylic polymer disclosed in PatentDocument 1 is used. Specifically, the compound (B), that is, the(meth)acrylic polymer is a polymer obtained by polymerizing apolymerizable unsaturated compound in the presence of catalysts, ametallocene compound represented by the following formula (1) and acrosslinkable silyl group-containing thiol compound. At least one end ofthe polymer is bonded to a residue (—S—R³) obtained by removing ahydrogen atom from the crosslinkable silyl group-containing thiolcompound used as a catalyst. Here, R³ represents a group having acrosslinkable silyl group.

The metallocene compound to be used as a polymerization catalyst can berepresented by the following formula (1):

[Formula 1]

In the formula (1), M represents a metal selected from the groupconsisting of metals of Groups 4, 5, and 14 of the periodic table,chromium, ruthenium, and palladium; specific examples of M includetitanium, zirconium, chromium, ruthenium, vanadium, palladium, and tin;R¹ and R² each independently represent at least one group selected fromthe group consisting of substituted or unsubstituted aliphatichydrocarbon groups, substituted or unsubstituted alicyclic hydrocarbongroups, substituted or unsubstituted aromatic hydrocarbon groups, andsubstituted or unsubstituted silicon-containing groups, a hydrogen atomor a single bond.

R¹ and R² may cooperate with each other to bond the two five-memberedrings of the compound represented by the formula (1) and the pluralityof adjacent groups R¹ or R² may cooperate with each other to form acyclic structure; a and b each independently represent an integer of 1to 4; Y represents a halogen atom or a hydrocarbon group in which atleast part of hydrogen atoms may be substituted with a halogen atom; andn is 0 or an integer obtained by subtracting 2 from the valence of themetal M.

Specific examples of the metallocene compound include: titanocenecompounds such as dicyclopentadiene-Ti-dichloride,dicyclopentadiene-Ti-bisphenyl,dicyclopentadiene-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl,dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophen-1-yl,dicyclopentadiene-Ti-bis-2,5,6-trifluorophen-1-yl,dicyclopentadiene-Ti-bis-2,6-difluorophen-1-yl,dicyclopentadiene-Ti-bis-2,4-difluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, anddimethylcyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyr-1-yl)-phen-1-yl;zirconocene compounds such as dicyclopentadienyl-Zr-dichloride,dicyclopentadiene-Zr-bisphenyl,dicyclopentadiene-Zr-bis-2,3,4,5,6-pentafluorophen-1-yl,dicyclopentadiene-Zr-bis-2,3,5,6-tetrafluorophen-1-yl,dicyclopentadiene-Zr-bis-2,5,6-trifluorophen-1-yl,dicyclopentadiene-Zr-bis-2,6-difluorophen-1-yl,dicyclopentadiene-Zr-bis-2,4-difluorophen-1-yl,dimethylcyclopentadienyl-Zr-bis-2,3,4,5,6-pentafluorophen-1-yl,dimethylcyclopentadienyl-Zr-bis-2,3,5,6-tetrafluorophen-1-yl,dimethylcyclopentadienyl-Zr-bis-2,6-difluorophen-1-yl, anddimethylcyclopentadienyl-Zr-bis-2,6-difluoro-3-(pyr-1-yl)-phen-1-yl;dicyclopentadienyl-V-chloride; bismethylcyclopentadienyl-V-chloride;bispentamethylcyclopentadienyl-V-chloride;dicyclopentadienyl-Ru-chloride; and dicyclopentadienyl-Cr-chloride.These metallocene compounds can be used singly or in combination of twoor more of them.

The metallocene compound can be used in a conventional catalytic amount.Specifically, the metallocene compound is generally used in an amount of1 to 0.001 parts by weight, preferably 0.01 to 0.005 parts by weight,per 100 parts by weight of a polymerizable unsaturated compound to bepolymerized.

The thiol compound to be used together with the metallocene compound inthe present invention is a thiol compound having a crosslinkable silylgroup. Such a crosslinkable silyl group-containing thiol compound is acompound generally represented by the following formula: HS—R³.

Here, R³ represents a group having a crosslinkable silyl group. Examplesof a crosslinkable silyl group to be used include the same crosslinkablesilyl groups as exemplified above with reference to the compound (A).Particularly, at least one crosslinkable silyl group selected from thegroup consisting of a hydroxysilyl group, a methoxysilyl group, anethoxysilyl group, a propoxysilyl group, a chlorosilyl group, and abromosilyl group is preferably used. Specific examples of R³ include3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane,3-mercaptopropyl-monomethyldimethoxysilane,3-mercaptopropyl-monophenyldimethoxysilane,3-mercaptopropyl-dimethylmonomethoxysilane,3-mercaptopropyl-monomethyldiethoxysilane,4-mercaptobutyl-trimethoxysilane, and 3-mercaptobutyl-trimethoxysilane.

It can be considered that when such a crosslinkable silylgroup-containing thiol compound is subjected to reaction, a hydrogenatom is removed from the thiol compound by mainly an organic metalcompound, and as a result a radical, —S—R³ is produced and is thenintroduced into at least one end of a resultant polymer. The activity ofthe crosslinkable silyl group introduced into the end of the polymer isnot lost due to the reaction, and the activity of the introduced silylgroup is maintained as it is.

As described above, removal of a hydrogen atom from the crosslinkablesilyl group-containing thiol compound, HS—R³ produces a radical, —S—R³,and the radical is bonded to a polymerizable unsaturated compound toactivate it, thereby initiating polymerization. At this time, themetallocene compound is used to remove a hydrogen atom from thecrosslinkable silyl group-containing thiol compound, HS—R³, therebyactivating the crosslinkable silyl group-containing thiol compound.Therefore, in a case where the crosslinkable silyl group-containingthiol compound is used singly, a conversion (a rate of polymerization)is significantly low, that is, substantially no reaction occurs betweenthe polymerizable unsaturated compounds in a case where thecrosslinkable silyl group-containing thiol compound is used singly. Asdescribed above, the metallocene compound is mainly used to activate thecrosslinkable silyl group-containing thiol compound, and usually existswith its original structure being maintained, that is, exists as acompound represented by the formula (1). However, there is a case wheresome of the metallocene compounds are bonded to the crosslinkable silylgroup-containing thiol compound, the polymerizable unsaturated compound,and derivatives thereof. Further, there is also a case where thisorganometallic compound is decomposed as the reaction proceeds so that areaction system contains a metal.

The amount of the crosslinkable silyl group-containing thiol compound tobe used can be appropriately determined according to the properties of atarget polymer. That is, when the concentration of the crosslinkablesilyl group-containing thiol compound in a reaction system is increased,not only a conversion per unit time but also a final conversion isincreased. At this time, an increase in the amount of the metallocenecompound increases the conversion per unit time, but does not exert alarge influence on the final conversion. Further, the amount of themetallocence compound to be used exerts little influence on themolecular weight of a resultant polymer, but the reaction does noteffectively proceed when the metallocene compound is not used.Furthermore, when the amount of the thiol compound to be used isincreased, the rate of polymerization becomes high. From the tendency,it can be considered that the metallocene compound to be used as one ofcatalysts for obtaining the compound (B) of the present invention hasthe function of an activation catalyst throughout the reaction, and thethiol compound to be used as the other catalyst for obtaining thecompound (B) of the present invention has the function of initiatingpolymerization (that is, functions as a polymerization initiatingspecies). As described above, it can be considered that the amount ofthe crosslikable silyl group-containing thiol compound to be used as acatalyst for obtaining the compound (B) of the present invention limitsthe molecular weight and the conversion.

Therefore, the amount of the crosslinkable silyl group-containing thiolcompound to be used can be appropriately determined according to, forexample, the molecular weight of a target polymer or the rate ofpolymerization, but the metallocene compound and the crosslinkable silylgroup-containing thiol compound are generally used in a mole ratio of100:1 to 1:50,000, preferably 10:1 to 1:10,000, to allow the reaction tosmoothly proceed and prevent runaway of the reaction.

The total amount of the crosslinkable silyl group-containing thiolcompound can be added at the initiation of the reaction. Alternatively,the crosslinkable silyl group-containing thiol compound may be added insuch a manner that a part of the total amount of the crosslinkable silylgroup-containing thiol compound is added at the initiation of thereaction and then the remaining crosslinkable silyl group-containingthiol compound is further added after the reaction is conducted for adesired period of time. In this case, the polymerizable unsaturatedcompound may also be added together with the remaining crosslinkablesilyl group-containing thiol compound. By further adding thecrosslinkable silyl group-containing thiol compound or by further addingthe crosslinkable silyl group-containing thiol compound together withthe polymerizable unsaturated compound, it is possible to increase theconversion.

As described above, the component (B) of the present invention, that is,the (meth)acrylic polymer can be obtained by reacting the polymerizableunsaturated compound by the use of the metallocene compound representedby the above specific formula (1) and the crosslinkable silylgroup-containing thiol compound. In the present invention, thecrosslinkable silyl group-containing thiol compound can be used togetherwith a thiol compound such as an alkyl thiol having no functional groupother than a thiol group (e.g., ethyl mercaptan, butyl mercaptan,hexylmercaptan, tertiary dodecyl mercaptan, normal dodecyl mercaptan,octyl mercaptan) or an aromatic thiol having no functional group otherthan a thiol group (e.g., phenyl mercaptan, benzyl mercaptan), a thiolcompound having a functional group in addition to a thiol group (e.g.,β-mercaptopropionic acid, mercaptoethanol, thiophenol), a polyfunctionalthiol compound obtained by esterifying trithioglycerin orpentaerythritol with β-mercaptopropionic acid or a polymeric thiolcontaining an active thiol group, such as a polysulfide-based polymer.

In the present invention, for the purpose of controlling the rate ofpolymerization and the degree of polymerization, a disulfide compound, atrisulfide compound or a tetrasulfide compound can be used in additionto the metallocene compound and the crosslinkable silyl group-containingthiol compound to be used as polymerization initiating catalysts.Examples of such disulfide, trisulfide and tetrasulfide compounds to beused as a polymerization controller include diethyl trisulfide, dibutyltetrasulfide, diphenyl disulfide, bis(2-hydroxyethyl) disulfide,bis(4-hydroxybutyl) tetrasulfide, bis(3-hydroxypropyl) trisulfide,bis(3-carboxypropyl) trisulfide, bis(3-carboxypropyl) tetrasulfide,bis(3-propyltrimethoxysilane) disulfide, andbis(3-propyltriethoxysilane) tetrasulfide. These sulfide compounds canbe used singly or in combination of two or more of them. Such a sulfidecompound can be used in such an amount that the polymerization accordingto the present invention is not deactivated. Specifically, the sulfidecompound is generally used in an amount of 50 to 0 parts by weight,preferably 20 to 0.005 parts by weight, per 100 parts by weight of thepolymerizable unsaturated compound to be polymerized.

The main chain of the component (B) of the present invention, that is,of the (meth)acrylic polymer is formed by polymerizing the polymerizableunsaturated compound as described below. Examples of such apolymerizable unsaturated compound include polymerizable unsaturatedcompounds represented by the following formulas (7) to (9).

[Formula 7]

In the formula (7), R⁴ to R⁶ each independently represent a hydrogenatom, a halogen atom or an alkyl group having 1 to 3 carbon atoms; andR⁷ represents a hydrogen atom, an alkali metal atom or a hydrocarbongroup having 1 to 22 carbon atoms (the hydrocarbon group may be linearor may have a side chain; at least part of hydrogen atoms of thehydrocarbon group or of a group constituting the side chain of thehydrocarbon group may be substituted with at least one polar group orreactive functional group selected from the group consisting of achlorine atom, a fluorine atom, a primary amino group, a secondary aminogroup, a tertiary amino group, a quaternary amine salt group, an amidogroup, an isocyanate group, an alkylene oxide group, a hydroxysilylgroup, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group,a chlorosilyl group, a buromosilyl group, and a glycidyl group; thehydrocarbon group may have a double bond; and the hydrocarbon group mayhave a cyclic structure). Specific examples of R⁷ include an alkylgroup, a cycloalkyl group, an aryl group, an alkenyl group, acycloalkenyl group, an alkoxy group, and an alkyl ether group. At leastpart of hydrogen atoms constituting the group R⁷ may be substitutedwith, for example, a halogen atom, a sulfonic acid group or a glycidylgroup.

[Formula 8]

In the formula (8), R¹¹ to R¹³ have the same meaning as the above R⁴ toR⁶, and R¹⁴ represents any of a hydroxyl group, —CO—NH₂, —CN, a glycidylgroup, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkenylgroup, an aryl group, an allyl ether group, and an alkyl ether group. Atleast part of hydrogen atoms constituting the group R¹⁴ may besubstituted with, for example, a halogen atom. Further, the group R¹⁴may be a group containing a structural unit derived from alkyleneglycol, a methylol group or an alkoxyamido group.

[Formula 9]

In the formula (9), R¹⁵ and R¹⁷ have the same meaning as the above R⁴ toR⁶, and R¹⁶ and R¹⁸ each independently represent any of a carboxylgroup, a hydroxyl group, —CO—NH₂, —CN, a glycidyl group, an alkyl group,an alkoxy group, an alkenyl group, a cycloalkenyl group, and an arylgroup. At least part of hydrogen atoms constituting the groups R¹⁶ andR¹⁸ may be substituted with, for example, a halogen atom. Further, thegroups R¹⁶ and R¹⁸ may cooperate with two carbon atoms bonded to R¹⁵ andR¹⁷ to form a cyclic structure, and the cyclic structure may have adouble bond.

Specific examples of such polymerizable unsaturated compounds include:acrylic acid and salts thereof such as alkali metal acrylates;methacrylic acid and salts thereof such as alkali metal methacrylates;alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate,propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate,2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate,and dodecyl acrylate; aryl esters of acrylic acid such as phenylacrylate and benzyl acrylate; alkoxyalkyl acrylates such as methoxyethylacrylate, ethoxyethyl acrylate, propoxyethyl acrylate, butoxyethylacrylate, and ethoxypropyl acrylate; alkyl esters of methacrylic acidsuch as methyl methacrylate, ethyl methacrylate, propyl methacrylate,butyl methacrylate, pentyl methacrylate, hexyl methacrylate,2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, decylmethacrylate, and dodecyl methacrylate; aryl esters of methacrylic acidsuch as phenyl methacrylate and benzyl methacrylate; alkoxyalkylmethacrylates such as methoxyethyl methacrylate, ethoxyethylmethacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, andethoxypropyl methacrylate; (poly)alkylene glycol diacrylates such asethylene glycol diacrylate, diethylene glycol diacrylate, triethyleneglycol diacrylate, polyethylene glycol diacrylate, propylene glycoldiacrylate, dipropylene glycol diacrylate, and tripropylene glycoldiacrylate; (poly)alkylene glycol dimethacrylates such as ethyleneglycol dimethacrylate, diethylene glycol dimethacrylate, triethyleneglycol dimethacrylate, polyethylene glycol dimethacrylate, propyleneglycol dimethacrylate, dipropylene glycol dimethacrylate, andtripropylene glycol dimethacrylate; polyacrylates such astrimethylolpropane triacrylate; polymethacrylates such astrimethylolpropane trimethacrylate; acrylonitrile; methacrylonitrile;vinyl acetate; vinylidene chloride; vinyl halide compounds such as2-chloroethyl acrylate and 2-chloroethyl methacrylate; acrylic acidesters of alicyclic alcohol such as cyclohexyl acrylate; methacrylicacid esters of alicyclic alcohol such as cyclohexyl methacrylate;oxazoline group-containing polymerizable compounds such as2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and2-isopropenyl-2-oxazoline; aziridine group-containing polymerizablecompounds such as acryloyl aziridine, methacryloyl aziridine,2-aziridinylethyl acrylate, and 2-aziridinylethyl methacrylate; epoxygroup-containing vinyl monomers such as allyl glycidyl ether, glycidylether acrylate, glycidyl ether methacrylate, glycidyl ether acrylate,2-ethylglycidyl ether acrylate, and 2-ethylglycidyl ether methacrylate;hydroxyl group-containing vinyl compounds such as 2-hydroxyethylacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,monoesters of acrylic acid or methacrylic acid and polypropylene glycolor polyethylene glycol, and adducts of lactons and 2-hydroxyethyl(meth)acrylate; fluorinated vinyl monomers such as fluorinated alkylmethacrylates and fluorinated alkyl acrylates; unsaturated carboxylicacids other than (meth)acrylic acid, such as itaconic acid, crotonicacid, maleic acid, and fumaric acid, salts thereof, (partial)estercompounds and anhydrides thereof, reactive halogen-containing vinylmonomers such as 2-chloroethyl vinyl ether and vinyl monochloroacetate;amido group-containing vinyl monomers such as methacrylamide,N-methylolmethacylamide, N-methoxyethylmethacrylamide, andN-butoxymethylmethacrylamide; and diene compounds such asethylidenenorbornene, isoprene, pentadiene, vinylcyclohexene,chloroprene, butadiene, methylbutadiene, cyclobutadiene andmethylbutadiene.

Other examples of the polymerizable unsaturated compound includemacromonomers having a radical polymerizable vinyl group at the end of avinyl-polymerized monomer (e.g., fluoromonomers, silicon-containingmonomers, macromonomers, styrene, silicone). These polymerizableunsaturated compounds can be used singly or in combination of two ormore of them. Further, these polymerizable unsaturated compounds may beliquid, solid or gaseous under reaction conditions, but a liquid monomeris preferably used for the reaction from the viewpoint of ease ofoperation.

As described above, the component (B) of the present invention, that is,the (meth)acrylic polymer is a polymer which can be obtained bypolymerizing the polymerizable unsaturated compound by variouspolymerization methods in the presence of a polymerization catalystcomposed of the metallocene compound and the crosslinkable silylgroup-containing thiol compound, and at least one molecular end of the(meth)acrylic polymer is bonded to —S—R³ obtained by removing a hydrogenbonded to a sulfur atom from the crosslinkable silyl group-containingthiol compound. As a result of polymerization of the polymerizableunsaturated compound as described above, a repeating unit representedby, for example, the following formulas (2), (10) and (11) are formed inthe main chain of the (meth)acrylic polymer depending on thepolymerizable unsaturated compound used.

[Formula 2]

In the formula (2), R⁴ to R⁶ each independently represent a hydrogenatom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, andR⁷ represents a hydrogen atom, an alkali metal atom or a hydrocarbongroup having 1 to 22 carbon atoms (the hydrocarbon atom may be linear ormay have a side chain; at least part of hydrogen atoms of thehydrocarbon group or of a group constituting the side chain of thehydrocarbon group may be substituted with at least one polar group orreactive functional group selected from the group consisting of achlorine atom, a fluorine atom, a primary amino group, a secondary aminogroup, a tertiary amino group, a quaternary amine salt group, an amidogroup, an isocyanate group, an alkylene oxide group, a hydroxysilylgroup, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group,a chlorosilyl group, a buromosilyl group, and a glycidyl group; thehydrocarbon group may have a double bond; and the hydrocarbon group mayhave a cyclic structure). Specific examples of R⁷ include an alkylgroup, a cycloalkyl group, an aryl group, an alkenyl group, acycloalkenyl group, an alkoxy group, and an alkyl ether group. At leastpart of hydrogen atoms constituting the group R⁷ may be substitutedwith, for example, a halogen atom, a sulfonic acid group or a glycidylgroup.

[Formula 10]

In the formula (10), R¹¹ to R¹³ have the same meaning as the above R⁴ toR⁶, and R¹⁴ represents any of a hydroxyl group, —CO—NH² group, —CNgroup, a glycidyl group, an alkyl group, an alkoxy group, an alkenylgroup, a cycloalkenyl group, an aryl group, an allyl ether group, and analkyl ether group. At least part of hydrogen atoms constituting thegroup R¹⁴ may be substituted with, for example, a halogen atom. Further,the group R¹⁴ may be a group containing a structural unit derived fromalkylene glycol, an alkoxysilyl group, an alkylalkoxysilyl group, amethylol group or an alkoxyamido group.

[Formula 11]

In the formula (11), R¹⁵ and R¹⁷ have the same meaning as the above R⁴to R⁶, and R¹⁶ and R¹⁸ each independently represent any of a carboxylgroup, a hydroxyl group, —CO—NH₂ group, —CN group, a glycidyl group, analkyl group, an alkoxy group, an alkenyl group, a cycloalkenyl group,and an aryl group. At least part of hydrogen atoms constituting thegroups R¹⁶ and R¹⁸ may be substituted with, for example, a halogen atom.Further, the groups R¹⁶ and R¹⁸ may cooperate with two carbon atomsbonded to R¹⁵ and R¹⁷ to form a cyclic structure, and the cyclicstructure may have a double bond.

The main chain of the component (B) of the present invention, that is,of the (meth)acrylic polymer is not particularly limited, but preferablycontains the repeating unit represented by the formula (2) in an amountof 50 to 100% by weight.

The component (B) of the present invention, that is, the (meth)acrylicpolymer may be produced by copolymerizing with a crosslinkable silylgroup-containing polymerizable unsaturated monomer [E]. Examples of thecrosslinkable silyl group include the same crosslinkable silyl groups asexemplified above with reference to the component (A). Particularly,such a crosslinkable silyl group is preferably at least one selectedfrom the group consisting of a hydroxysilyl group, a methoxysilyl group,an ethoxysilyl group, a propoxysilyl group, a chlorosilyl group, and abromosilyl group. The crosslinkable silyl group-containing polymerizableunsaturated monomer [E] usable in the present invention can berepresented by, for example, the following formula (12):

[Formula 12]

In the above formula, R²¹ and R²³ have the same meaning as the above R⁴to R⁶; R²² represents any group or atom selected from a hydrogen atom, ahalogen atom, —CN group, a glycidyl group, an alkyl group, an alkoxygroup, an alkenyl group, a cycloalkenyl group, an aryl group, an allylether group, an alkyl ether group, an alkoxysilyl group, and analkylalkoxysilyl group; when R²² is a group other than a hydrogen atomand a halogen atom, at least part of hydrogen atoms constituting thegroup R²² may be substituted with, for example, a halogen atom; R²² maybe a group containing a structural unit derived from alkylene glycol, analkoxysilyl group, an alkylalkoxysilyl group, a methylol group or analkoxyamido group; R²⁴ is a bivalent group such as —CO—O—, —CH₂—,—C₂H₄—, —CO—O—C₂H₄— or —CO—O—C₂H₄—O—, or a single bond; and R²⁵, R²⁶,and R²⁷ each independently represent any of an alkyl group, an alkoxygroup, a hydrogen atom, and a halogen atom.

By copolymerizing with the compound represented by the formula (12), itis possible to introduce a repeating unit represented by the followingformula (13) into the main chain:

[Formula 13]

(In the formula (13), R²¹ to R²⁷ have the same meaning as described withreference to the formula (12).)

The repeating unit represented by the formula (13) is preferablyintroduced into the main chain of the component (B) of the presentinvention, that is, of the (meth)acrylic polymer in an amount of 1 to50% by weight, particularly preferably 5 to 30% by weight, in terms ofmonomer based on the amount of the total repeating units. By introducingthe repeating unit (13) into the main chain of the (meth)acrylic polymer(B) in such an amount, it is possible to impart self-reactive curabilityto the (meth)acrylic polymer (B). In addition, it is also possible forthe (meth)acrylic polymer (B) to react with a silane coupling agenthaving a crosslinkable alkoxysilyl group, a silanol compound, a metalalkoxide such as tetraethoxy titanium, a metal chelate such as a metalalkolate or a resin composition having an alkoxysilyl group, such as asilicone resin to form an excellent cured body. It is to be noted thatthe repeating unit represented by the formula (13) can be introduced notonly by using the crosslinkable silyl group-containing polymerizableunsaturated monomer [E] but also after having prepared a (meth)acrylicpolymer by reacting the obtained (meth)acrylic polymer with acrosslinkable silyl group-containing compound.

Examples of the monomer [E] capable of forming a repeating unitrepresented by the formula (13) include: vinyl compound monomers inwhich a crosslinkable silyl group is directly introduced into a vinylgroup, such as vinyltrimethoxy silane, γ-vinyl-monochlorodimethoxysilane, γ-vinyl-trichloro silane, and γ-vinyl-dichloro-monomethylsilane; (meth)acrylic monomers in which a crosslinkable silyl group isintroduced into a highly reactive (meth)acryloyl group, such asγ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, γ-methacryloxypropyl monomethyldimethoxy silane, andγ-acryloxypropyl trimethoxy silane; and polymerizable monomers in whicha crosslinkable silyl group is introduced into a compound having apolymerizable unsaturated group, such as allyltrimethoxysilane andtrimethoxysilylpropylallylamine.

The (meth)acrylic polymer (B), especially the (meth)acrylic polymerhaving a repeating unit represented by the formula (13) can be producedby (co)polymerizing the polymerizable unsaturated compound describedabove in the presence of the compound represented by the formula (1) andthe crosslinkable silyl group-containing thiol compound. Such a reactioncan be carried out regardless of the presence or absence of a solvent ordispersion medium, but nonaqueous polymerization is preferably employedfrom the viewpoint of stability of crosslinkable silyl groups.

The polymerization reaction is generally carried out in an inert gasatmosphere under conditions where a conventional radical polymerizationis carried out. Therefore, an active gas such as oxygen is not presentin the polymerization reaction system. Examples of an inert gas to beused include a nitrogen gas, an argon gas, a helium gas and a carbonicacid gas. As described above, the component (B) of the present inventionis a polymer obtained by polymerizing the polymerizable unsaturatedcompound in the presence of the specific organic metal compound and thecrosslinkable silyl group-containing thiol compound, and at least oneend of the thus obtained polymer (in most cases, almost all of the endsof the polymer) is bonded to a residue (—S—R³) obtained by removing ahydrogen atom bonded to a sulfur atom from the crosslinkable silylgroup-containing thiol compound.

In such polymerization, a polymerization catalyst composed of themetallocene compound represented by the formula (1) and thecrosslinkable silyl group-containing thiol compound can be used in acatalytic amount generally employed, but the metallocene compoundrepresented by the formula (1) is generally used in an amount of0.0000001 to 0.0001 mol per mol of an unsaturated group of thepolymerizable unsaturated compound, preferably in such an amount thatthe mole ratio of the metallocene compound and the crosslinkable silylgroup-containing thiol compound is in the range of 10:1 to 1:10,000 inaccordance with the number of moles of the crosslinkable silylgroup-containing thiol compound to be used. The crosslinkable silylgroup-containing thiol compound is generally used in an amount of0.00001 to 0.7 mol, preferably 0.0001 to 0.5 mol.

Such a polymerization reaction can be carried out with heating, warmingor cooling according to the kind of polymerizable unsaturated compoundto be used, but the polymerization reaction temperature is preferablyset in the range of 0 to 150° C., particularly preferably in the rangeof 25 to 120° C. By setting the polymerization reaction temperature to avalue within the above range, it is possible to allow the reaction tostably proceed without runaway of reaction. The reaction temperaturedepends on the activity of an unsaturated group of the polymerizableunsaturated compound to be used. However, even in a case where a(meth)acrylic ester-based polymerizable unsaturated compound havingrelatively high polymerizability, if the reaction temperature is set at0° C. or lower, the catalytic activity of the metallocene compoundrepresented by the formula (1) and the crosslinkable silylgroup-containing thiol compound is decreased so that the time requiredfor achieving a sufficient conversion is prolonged, thereby reducingefficiency. On the other hand, even in a case where a compound havinglow polymerizability such as styrene-type unsaturated compound is used,a satisfactory conversion can be achieved as long as the reactiontemperature is set at 25° C. or higher.

If the reaction temperature is set 150° C. or higher, there is a dangerof runaway reaction attributed to significant heat generation during thepolymerization reaction. On the other hand, by setting thepolymerization reaction temperature at 120° C. or lower, it is possibleto maintain a smooth progress of the reaction without runaway of thereaction. In the polymerization according to the present invention, thereaction time can be appropriately set in view of, for example,conversion and molecular weight, but for example, the reaction time isgenerally set in the range of 2 to 12 hours, preferably in the range of2 to 8 hours under the above conditions.

The polymerization reaction can be terminated by lowering thetemperature of the reaction mixture or preferably by adding apolymerization terminator such as benzoquinone. By carrying outpolymerization in the above manner, it is possible to obtain a polymergenerally having a conversion of 40% or higher, preferably 60% orhigher. The weight average molecular weight (Mw) of the thus obtainedpolymer measured by gel permeation chromatography (GPC) is generally inthe range of 500 to 1,000,000, preferably in the range of 1,000 to300,000, and the number average molecular weight (Mn) is generally inthe range of 500 to 1,000,000, preferably in the range of 1,000 to100,000. Further, the dispersion index of the polymer (weight averagemolecular weight/number average molecular weight) is generally in therange of 1.02 to 9.0, preferably in the range of 1.2 to 3.0.

In a case where a deliming process is not performed, the component (B)of the present invention, that is, the polymer obtained bypolymerization using the polymerization catalyst also contains anorganic metal compound. Further, a sulfur-containing group derived fromthe thiol used is bonded to at least part of the molecular ends of theobtained polymer. In the polymerization reaction using the catalystdescribed above, the crosslinkable silyl group-containing thiol compoundis used as a polymerization initiating species, but generally such acrosslinkable silyl group-containing thiol compound does not haveactivity as polymerization initiating species when used singly. However,in a case where the organometallic compound represented by the formula(1) is used together with the crosslinkable silyl group-containing thiolcompound, a crosslinkable silyl group-containing thiol group derivedfrom the crosslinkable silyl group-containing thiol compound isconverted into an active species capable of initiating polymerization bythe organometallic catalyst, to thereby become an initiating species formonomers. Therefore, in this reaction, the conversion per unit time isenhanced by an increase in the amount of the crosslinkable silylgroup-containing thiol compound relative to the amount of monomer. Asulfur-containing group derived from the crosslinkable silylgroup-containing thiol compound used is bonded to the polymerizationinitiation terminal of the obtained polymer. However, the crosslinkablesilyl group-containing thiol compound used functions not only as apolymerization initiating species but also as a chain transfer agent,and therefore the molecular weight (degree of polymerization) and theconversion greatly depend on the amount of the crosslinkable silylgroup-containing thiol compound. From these phenomena, it can besupposed that the progress and termination of polymerization in thisreaction are those of radical polymerization. The thio-radical (—S) ofthe crosslinkable silyl group-containing thiol compound from which ahydrogen atom is removed by chain transfer again functions as apolymerization initiating species and attacks the monomer. Therefore, asulfur-containing group derived from the crosslinkable silylgroup-containing thiol compound used is bonded to the terminal of apolymer obtained by this polymerization method, irrespective of theamount of the crosslinkable silyl group-containing thiol compound used.

In the reaction system of the component (B) of the present invention,polymerization can be carried out in the same manner as in solutionpolymerization or bulk polymerization in a polar organic solvent such asan alcohol or in a dispersion medium such as water. Therefore, it can beconsidered that a radical reaction is predominant in the polymerizationreaction according to the present invention. Accordingly, it can beconsidered that the reaction termination end of an obtained polymer ishydrogen removed from the silyl group-containing thiol compound due tochain transfer, or thiols having a thio-radical converted into a radicaland a sulfur-containing group derived from the silyl group-containingthiol compound due to radical coupling with a growing polymer radical.

In the obtained polymer, the metallocene compound remains with itsoriginal form being maintained, or is bonded to another organic group,or remains in the form of metal. On the other hand, the crosslinkablesilyl group-containing thiol compound directly contributes to thereaction of forming a polymer, and the reaction proceeds while thecrosslinkable silyl group-containing thiol compound itself is beingdecomposed so that a terminal group derived from the crosslinkable silylgroup-containing thiol compound is introduced into the polymer end.

The activity of a crosslinkable silyl group in a group which is derivedfrom the crosslinkable silyl group-containing thiol compound and isbonded to the polymer end is not lost due to the polymerizationreaction, and is retained in an obtained polymer. The estimation andprogress of the reaction are believed to the most rational by theinventors based on various phenomena occurring in the reaction accordingto the present invention, which naturally in no way limits the presentinvention.

As the component (B) of the present invention, a (meth)acrylic polymer(B1) is particularly preferable. Specifically, the (meth)acrylic polymer(B1) contains a (meth)acrylic polymer obtained by polymerizing a(meth)acrylic monomer having a polymerizable unsaturated bond in thepresence of the metallocene compound represented by the formula (1) anda thiol compound containing at least one crosslinkable silyl group inthe molecule, at least one end of the (meth)acrylic polymer being bondedto a residue, —S—R³ (where R³ represents a group having a crosslinkablesilyl group) obtained by removing a hydrogen atom from the thiolcompound, and the main chain of the (meth)acrylic polymer contains arepeating unit represented by the formula (2) in an amount of 99% byweight or less, preferably 95 to 70% by weight and further contains as arepeating unit other than the repeating unit represented by the formula(2), a repeating unit derived from the polymerizable unsaturatedcompound (E) containing at least one crosslinkable silyl group in themolecule, in an amount of 1 to 50% by weight, preferably 5 to 30% byweight.

In addition to the repeating unit represented by the formula (2) and therepeating unit derived from the polymerizable unsaturated compoundmonomer represented by the formula (12), the (meth)acrylic polymer (B1)may further contain, for example, a repeating unit represented by theformulae (10) and (11) or a repeating unit derived from another monomercontaining a reactive unsaturated bond, such as a dimer or trimer ofethylene or propylene. The amount of the repeating unit derived fromanother monomer to be copolymerized is usually 0 to 40% by weight,preferably 0 to 20% by weight. It is to be noted that the amount of eachof the repeating units to be copolymerized in the (co)polymer is basedon a total of 100% by weight.

The weight average molecular weight (Mw) of the (meth)acrylic polymer(B1) measured by gel permeation chromatography is generally in the rangeof 500 to 1,000,000, preferably in the range of 1,000 to 300,000, andthe number average molecular weight (Mn) is generally in the range of500 to 1,000,000, preferably in the range of 1,000 to 100,000. Further,the dispersion index (weight average molecular weight/number averagemolecular weight) of the (meth)acrylic polymer (B1) is generally in therange of 1.02 to 9.0, preferably in the range of 1.2 to 3.0.

Such a (meth)acrylic polymer (B1) is generally a viscous liquid whencontaining a solvent or including a resin content only, but is cured byreaction in the presence of a blended curing agent or the like. The thusobtained cured product has elasticity and plasticity. The crosslinkablesilyl group derived from the formula (12) and introduced into the mainchain of the (meth)acrylic polymer (B1) including the repeating unitsdescribed above and having a component unit derived from the silylgroup-containing thiol compound at the end thereof and the crosslinkablesilyl group introduced into the molecular end of the (meth)acrylicpolymer (B1) are highly reactive, and therefore the (meth)acrylicpolymer (B1) is cured by self-condensation reaction, condensationcrosslinking reaction, or combination of self-condensation reaction andcondensation crosslinking reaction.

The blending ratio of the component (B) is not particularly limited, butis preferably 0.01 to 100 parts by weight, particularly preferably 0.1to 90 parts by weight, per 1 part by weight of the component (A). These(meth)acrylic polymers can be used singly or in combination of two ormore of them.

It is preferred that the curable composition of the present invention isfurther mixed with a component (C), that is, a curing catalyst. Examplesof the curing catalyst as the component (C) include, but are not limitedto, organometallic compounds and amines. Particularly, a silanolcondensation catalyst is preferably used. Examples of the silanolcondensation catalyst include: organotin compounds such as stannousoctoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate,dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide,dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltindilaurate, dioctyltin diversatate, tin octylate, and tin naphthenate;organotin compounds (C1) represented by the following general formnula(5); reaction products of dibutyltin oxide with phthalate esters;titanates such as tetrabutyl titanate and tetrapropyl titanate;organoaluminum compounds such as aluminum trisacetylacetonate, aluminumtrisethylacetoacetate, and diisopropoxy aluminum ethylacetoacetate;chelate compounds such as zirconium tetraacetylacetonate and titaniumtetraacetylacetonate; organic acid salts of lead such as lead octylateand lead naphthenate; organic acid salts of bismuth such as bismuthoctylate, bismuth neodecanoate, and bismuth rosinate; and other acidcatalysts and basic catalysts well known as silanol condensationcatalysts:

[Formula 5]R⁹R¹⁰SnO  (5)

In the formula (5), R⁹ and R¹⁰ each represent a monovalent hydrocarbongroup. Preferred examples of R⁹ and R¹⁰ include, but are not limited to,monovalent hydrocarbon groups having about 1 to 20 carbon atoms such asmethyl, ethyl, propyl, butyl, amyl, dodecyl, lauryl, propenyl, phenyl,and tolyl groups. R⁹ and R¹⁰ may be the same or different. Particularlypreferred examples of the organotin compound (C1) represented by thegeneral formula (5) include dialkyltin oxides such as dimethyltin oxide,dibutyltin oxide, and dioctyltin oxide.

In a case where the organotin compound (C1) represented by the generalformula (5) is used as the component (C), the curable compositioncontaining at least the components (A), (B) and (C1) and being packed ina hermetically sealed container is preferably subjected to reactiontreatment to develop quick curability. The reaction treatment is carriedout in the same manner as in the manufacturing method of the curablecomposition of the present invention described later.

The blending ratio of the component (C) is preferably 0.1 to 30 parts byweight, particularly preferably 0.5 to 20 parts by weight, per 100 partsby weight of the component (A) from the viewpoint of, for example, acrosslinking rate and the physical properties of a cured product. Thesecuring catalysts can be used singly or in combination of two or more ofthem.

It is preferred that the curable composition of the present inventionfurther contain a component (D), that is, a silane coupling agent fromthe viewpoint of improvement in adhesion properties and acceleration ofcuring. Examples of such a silane coupling agent include, but are notlimited to, well-known ones, for example, aminosilanes such asaminoethylaminopropyltrimethoxysilane,aminoethylaminopropylmethyldimethoxysilane, andaminoethylaminopropylmethylmethoxysilane, epoxysilanes such asγ-glycidoxypropyltrimethoxysilane, (meth)acrylic silanes such asγ-methacryloxypropyltrimethoxysilane, mercaptosilanes such asγ-mercaptopropyltrimethoxysilane, and isocyanate silanes such asγ-isocyanatepropyltrimethoxysilane.

The blending ratio of the component (D) is not particularly limited, butis preferably about 0.1 to 30 parts by weight, more preferably 0.3 to 15parts by weight, per 100 parts by weight of the component (A). Thesesilane coupling agents can be used singly or in combination of two ormore of them.

If necessary, the curable composition of the present invention may befurther mixed with various materials such as physicalproperty-modifiers, fillers, plasticizers, thixotropic agents,dehydrating agents (storage stability improvers), tackifiers,anti-sagging agents, ultraviolet absorbers, antioxidants, flameretardants, coloring agents, and radical polymerization initiators, inaddition to the above-described components, or may be blended withvarious solvents such as toluene and alcohol or with other compatiblepolymers.

The physical property-modifier is added to improve tensile properties.Examples of the physical property-modifier include: silicon compoundshaving one silanol group in one molecule, such as triphenylsilanol,trialkylsilanol, dialkylphenylsilanol, and diphenylalkylsilanol; andvarious silane coupling agents such as silicon compounds producing acompound having one silanol group in one molecule by hydrolysis, such astriphenylmethoxysilane, trialkylmethoxysilane,dialkylphenylmethoxysilane, diphenylalkylmethoxysilane,triphenylethoxysilane, and trialkylethoxysilane. These physicalproperty-modifiers can be used singly or in combination of two or moreof them.

The filler is added to reinforce a cured product. Examples of such afiller include calcium carbonate, magnesium carbonate, diatomite,hydrous silicic acid, silicic acid anhydride, calcium silicate, silica,titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin,and zeolite. Among them, calcium carbonate is preferably used, andcalcium carbonate treated with fatty acid is more preferably used.Alternatively, glass beads, silica beads, alumina beads, carbon beads,styrene beads, phenol beads, acrylic beads, porous silica, shirasuballoon, glass balloon, silica balloon, saran balloon, or acrylicballoon may also be used. Among them, acrylic balloon is preferably usedfrom the viewpoint of less reduction in elongation of a curedcomposition. These fillers can be used singly or in combination of twoor more of them.

The plasticizer is added to improve the elongation properties of a curedproduct and achieve low modulus. Examples of such a plasticizer include:esters of phosphoric acid such as tributyl phosphate and tricresylphosphate; esters of phthalic acid such as dioctyl phthalate (DOP),dibutyl phthalte, and butylbenzyl phthalate; esters of fatty monobasicacids such as glycerol monooleate; esters of fatty dibasic acids such asdibutyl adipate and dioctyl adipate; glycol esters such as polypropyleneglycol; aliphatic esters; epoxy plasticizers; polyester-basedplasticizers; polyethers; polystyrenes; and acrylic plasticizers. Theseplasticizers can be used singly or in combination of two or more ofthem.

Examples of the thixotropic agent include inorganic thixotropic agentssuch as colloidal silica and asbestos powder, organic thixotropic agentssuch as organic bentonite, modified polyester polyols, and fatty acidamides, hydrogenated castor oil derivatives, fatty acid amide waxes,aluminum stearate, and barium stearate. These thixotropic agents can beused singly or in combination of two or more of them.

The dehydrating agent is added to remove moisture during storage.

Examples of the dehydrating agent include silane compounds such asvinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane,methyltrimethoxysilane, and methyltriethoxysilane.

The antioxidant is used to in order to prevent oxidation of curedsealants, thereby improving weatherability thereof. Examples of such anantioxidant include hindered amine-based antioxidants and hinderedphenol-based antioxidants. Examples of hindered amine-based antioxidantsinclude, but are not limited to,N,N′,N″,N′″-tetrakis-(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine,a polycondensate of dibutylamine, 1,3,5-triazine,N,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine, andN-(2,2,6,6-tetramethyl-4-piperidyl)butylamine,poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}],a polymer of dimethyl succinate with4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, [decanedioic acidbis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl)ester, a reactionproduct of 1,1-dimethylethylhydroperoxide and octane(70%)]-polypropylene (30%),bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate,methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl(propionyloxy)-2,2,6,6-tetramethylpiperidine,4-benzoyloxy-2,2,6,6-tetramethylpiperidine, and8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione.Examples of hindered phenol-based antioxidants include, but are notlimited to,pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)],benzenepropanoic acid,3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9-branched alkyl ester,2,4-dimethyl-6-(1-methylpentadecyl)phenol,diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate,3,3′,3″,5,5′,5″-hexa-tert-butyl-4-a,a′,a″-(mesitylene-2,4,6-triyl)tri-p-cresol,calciumdiethylbis[[[3,5-bis-(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate],4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate],hexamethylene bis[3-(3,5-di-tert-butyl--4-hydroxyphenyl)propionate],1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trione, a reaction product of N-phenylbenzeneamine with2,4,4-trimethylpentene, and2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol.These antioxidants can be used singly or in combination of two or moreof them.

The ultraviolet absorber is used to prevent photo deterioration of acured sealing material and to improve weatherability of the curedsealing material, and includes examples thereof benzotriazole-based,triazine-based, benzophenone-based, and benzoate-based ultravioletabsorbers. Examples of the ultraviolet absorber include, but are notlimited to, benzotriazole-based ultraviolet absorbers such as2,4-di-tert-butyl-6-(5-chlorobenzotriazole-2-yl)phenol,2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol,2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, a reactionproduct of methyl3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate/polyethyleneglycol 300; triazol-based ultraviolet absorbers such as2-(2H-benzotriazole-2-yl)-6-(linear and brancheddodecyl)-4-methylphenol; triazine-based ultraviolet absorbers such as2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol;benzophenone-based ultraviolet absorbers such as octabenzone; andbenzoate-based ultraviolet absorbers such as2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate. Theseultraviolet absorbers can be used singly or in combination of two ormore of them.

A second embodiment of the curable composition of the present inventionincludes the crosslinkable silyl group-containing organic polymer (A)and the organotin compound (C1) represented by the following generalformula (5):

[Formula 5]R⁹R¹⁰SnO  (5)

(wherein R⁹ and R¹⁰ each represent a monovalent hydrocarbon group.)

The component (A) is the same as that described above with reference tothe first embodiment of the curable composition of the presentinvention. It is to be noted that the crosslinkable silylgroup-containing (meth)acrylic polymer (B) as disclosed in PatentDocument 1 may be used as the component (A). The component (C1) is alsothe same as that described above with reference to the first embodimentof the curable composition of the present invention, and the component(C1) is blended in the same ratio as described above with reference tothe first embodiment of the curable composition of the presentinvention. The same materials as described above with reference to thefirst embodiment other than the above components can also be blendedwith the curable composition.

The curable composition of the present invention is not particularlylimited, but is preferably produced by the production method of thepresent invention from the viewpoint of the acceleration of developmentof curing properties. According to the production method of the curablecomposition of the present invention, the curable composition containingat least the polymer (A) and the organotin compound (C1) as a curingcatalyst is packed in a hermetically sealed container, and is thensubjected to reaction treatment to develop quick curability.

The reaction treatment to develop quick curability is not particularlylimited. For example, the curable composition may be preserved at a lowtemperature to room temperature until quick curing curability isdeveloped, or may be subjected to heat treatment. The heat treatment ispreferably carried out at 30 to 150° C. for 30 minutes to 3 days. Thecurable composition of the present invention using the organotincompound (C1) as the curing catalyst (C) has high production stabilityand is gradually cured. Generally, the curable composition of thepresent invention exhibits its inherent quick curability after storageat room temperature in about one month, but the development of curingproperties can be significantly accelerated by the heat treatment. Theheat treatment is appropriately carried out depending on the situation.

EXAMPLE

Hereinafter, the present invention will be described in more detail withreference to the following Examples. However, it goes without sayingthat these Examples are illustrative only and not intended to limit thepresent invention.

Synthesis Example 1

43 parts by weight of xylene, 80 parts by weight of methylmethacrylate,20 parts by weight of stearylmethacrylate, 20 parts by weight ofγ-methacryloxypropyltrimethoxysilane, and 0.1 parts by weight ofruthenocene dichloride as a metal catalyst were placed in a flaskequipped with a stirrer, a nitrogen gas introduction tube, athermometer, and a reflux cooling tube. The flask contents were heatedto 80° C. while a nitrogen gas was being introduced into the flask.

Then, 20 parts by weight of 3-mercaptopropyltrimethoxysilanesufficiently purged with a nitrogen gas was fed into the flask at onceunder stirring. After the completion of addition of 20 parts by weightof the 3-mercaptopropyltrimethoxysilane, the flask contents understirring were heated or cooled for 4 hours so that the temperature ofthe flask contents was maintained at 80° C. Further, another 20 parts byweight of 3-mercaptopropyltrimethoxysilane sufficiently purged with anitrogen gas was fed into the flask in 5 minutes under stirring. Afterthe completion of addition of another 20 parts by weight of the3-mercaptopropyltrimethoxysilane, reaction was carried out for 4 hourswhile the flask contents were cooled and heated so that the temperatureof the flask contents under stirring was maintained at 90° C.

After the completion of the reaction carried out in the above manner for8 hours and 5 minutes in total, an obtained reaction product was cooledto room temperature, and then 20 parts by weight of a benzoquinonesolution (95% THF solution) was added to the reaction product toterminate polymerization. Further, as the crosslinkable silylgroup-containing organic polymer (A), 150 parts by weight of SilylSAT-200 manufactured by KANEKA CORPORATION (crosslinkable silylgroup-containing polyoxyalkylene-based polymer; crosslinkable silylgroup: methyldimethoxysilyl group) was added to the reaction product.

The thus obtained reaction product was transferred into an evaporator,and was gradually heated to 80° C. under a reduced pressure to removexylene, THF, and the remaining monomers and thiol compound. As a result,a mixture 1 of a crosslinkable silyl group-containingpolyoxyalkylene-based polymer (A) and a (meth)acrylic polymer (B) wasobtained.

Synthesis Example 2

Synthesis was carried out in the same manner as in Synthesis Example 1except that 10 parts by weight of normal butyl acrylate and 70 parts byweight of methylmethacrylate were placed in the flask instead of 80parts by weight of methylmethacrylate. As a result, a mixture 2 of acrosslinkable silyl group-containing polyoxyalkylene-based polymer (A)and a (meth)acrylic polymer (B) was obtained.

Synthesis Example 3

Synthesis was carried out in the same manner as in Synthesis Example 1except that 10 parts by weight of normal butyl acrylate, 70 parts byweight of methylacrylate, and 20 parts by weight of stearylacrylate wereplaced in the flask instead of 43 parts by weight of xylene, 80 parts byweight of methylmethacrylate, and 20 parts by weight ofstearylmethacrylate. As a result, a mixture 3 of a crosslinkable silylgroup-containing polyoxyalkylene-based polymer (A) and a (meth)acrylicpolymer (B) was obtained.

Synthesis Example 4

Synthesis was carried out in the same manner as in Synthesis Example 3except that 150 parts by weight of ES-GX3440ST manufactured by ASAHIGLASS Co., Ltd. (crosslinkable silyl group-containingpolyoxyalkylene-based polymer; crosslinkable silyl group:trimethoxysilyl group) was fed into the flask as a crosslinkable silylgroup-containing organic polymer (A) instead of 150 parts by weight ofSilyl SAT-200 (crosslinkable silyl group: methyldimethoxysilyl group).As a result, a mixture 4 of a crosslinkable silyl group-containingpolyoxyalkylene-based polymer (A) and a (meth)acrylic polymer (B) wasobtained.

Synthesis Example 5

Synthesis was carried out in the same manner as in Synthesis Example 3except that 75 parts by weight of Silyl SAT-200 (crosslinkable silylgroup: methyldimethoxysilyl group) and 75 parts by weight of ES-GX3440ST(crosslinkable silyl group: trimethoxysilyl group) were fed into theflask as a crosslinkable silyl group-containing organic polymer (A)instead of 150 parts by weight of Silyl SAT-200 (crosslinkable silylgroup: methyldimethoxysilyl group). As a result, a mixture 5 of acrosslinkable silyl group-containing polyoxyalkylene-based polymer (A)and a (meth)acrylic polymer (B) was obtained.

Synthesis Example 6

Synthesis was carried out in the same manner as in Synthesis Example 3except that 150 parts by weight of Silyl MA-440 manufactured by KANEKACORPORATION (crosslinkable silyl group-containing (meth)acrylic-modifiedpolyoxyalkylene-based polymer; crosslinkable silyl group:methyldimethoxysilyl group) was fed into the flask as a crosslinkablesilyl group-containing organic polymer (A) instead of 150 parts byweight of Silyl SAT-200 (crosslinkable silyl group: methyldimethoxysilylgroup). As a result, a mixture 6 of a crosslinkable silylgroup-containing (meth)acrylic-modified polyoxyalkylene-based polymer(A) and a (meth)acrylic polymer (B) was obtained.

Comparative Synthesis Example 1

43 parts by weight of xylene, 80 parts by weight of methylmethacrylate,20 parts by weight of stearylmethacrylate, 20 parts by weight ofγ-methacryloxypropyltrimethoxysilane, and 0.1 part by weight ofruthenocene dichloride as a metal catalyst were placed in a flaskequipped with a stirrer, a nitrogen gas introduction tube, athermometer, and a reflux cooling tube. The flask contents were heatedto 80° C. while a nitrogen gas was introduced into the flask.

Then, 20 parts by weight of 3-mercaptopropyltrimethoxysilanesufficiently purged with a nitrogen gas was fed into the flask at onceunder stirring. After the completion of addition of 20 parts by weightof the 3-mercaptopropyltrimethoxysilane, the flask contents understirring were heated or cooled for 4 hours so that the temperature ofthe flask contents was maintained at 80° C. Further, another 20 parts byweight of 3-mercaptopropyltrimethoxysilane sufficiently purged with anitrogen gas was fed into the flask for 5 minutes under stirring. Afterthe completion of addition of another 20 parts by weight of the3-mercaptopropyltrimethoxysilane, reaction was carried out for 4 hourswhile the flask contents were cooled or heated so that the temperatureof the flask contents under stirring was maintained at 90° C.

After the completion of the reaction carried out in the above manner for8 hours and 5 minutes in total, an obtained reaction product was cooledto room temperature, and then 20 parts by weight of a benzoquinonesolution (95% THF solution) was added to the reaction product toterminate polymerization.

The thus obtained reaction product was transferred into an evaporator,and was gradually heated to 80° C. under a reduced pressure to removeTHF and the remaining monomers and thiol compound. As a result, a(meth)acrylic polymer 1(B) was obtained.

Comparative Synthesis Example 2

Synthesis was carried out in the same manner as in Comparative SynthesisExample 1 except that 10 parts by weight of normal butyl acrylate and 70parts by weight of methylmethacrylate were placed in the flask insteadof 80 parts by weight of methylmethacrylate. As a result, a(meth)acrylic polymer 2(B) was obtained.

Comparative Synthesis Example 3

Synthesis was carried out in the same manner as in Comparative SynthesisExample 1 except that 10 parts by weight of normal butyl acrylate, 70parts by weight of methylacrylate, and 20 parts by weight ofstearylacrylate were placed in the flask instead of 43 parts by weightof xylene, 80 parts by weight of methylmethacrylate, and 20 parts byweight of stearylmethacrylate. As a result, a (meth)acrylic polymer 3(B)was obtained.

Comparative Synthesis Example 4

45 parts by weight of xylene heated to 110° C., 80 parts by weight ofmethylmethacrylate, 20 parts by weight of stearylmethacrylate, 2.5 partsby weight of γ-methacryloxypropyltrimethoxysilane, and 2.1 parts byweight of 3-mercaptopropyltrimethoxysilane were placed in a flask, andthen a solution in which 7.4 parts by weight of azobisisobutyronitrilewas dissolved was dropped as a polymerization initiator into the flaskfor 6 hours. After 2 hours passed from the completion of dropping of thesolution, polymerization was carried out, and 150 parts by weight ofSilyl SAT-200 (crosslinkable silyl group: methyldimethoxysilyl group)was added thereto as a crosslinkable silyl group-containingpolyoxyalkylene-based polymer (A).

The thus obtained reaction product was transferred into an evaporator,and was then gradually heated to 80° C. under a reduced pressure toremove xylene and the remaining monomers thereby to obtain a mixture 7of the crosslinkable silyl group-containing polyoxyalkylene-basedpolymer (A) and a (meth)acrylic polymer.

Example 1

As shown in Table 1, the mixture 1 of a crosslinkable silylgroup-containing polyoxyalkylene polymer (A) and a crosslinkable silylgroup-containing (meth)acrylic polymer (B) obtained in Synthesis Example1, vinyltrimethoxysilane, an aminosilane compound, and No. 918 (that isa reaction product of dibutyltin oxide with phthalate) as a curingcatalyst (C) were blended in their respective predetermined amountsshown in Table 1 to prepare a curable composition.

TABLE 1 Comparative Examples Examples 1 2 3 4 5 6 7 1 2 3 Mixture 1(A) + (B) *1 100 — — — — — 100 — — — Mixture 2 (A) + (B) *2 — 100 — — —— — — — — Mixture 3 (A) + (B) *3 — — 100 — — — — — — — Mixture 4 (A) +(B) *4 — — — 100 — — — — — — Mixture 5 (A) + (B) *5 — — — — 100 — — — —— Mixture 6 (A) + (B) *6 — — — — — 100 — — — — (Meth)acrylic polymer1(B) *7 — — — — — — — 143 — — (Meth)acrylic polymer 2(B) *8 — — — — — —— — 143 — (Meth)acrylic polymer 3(B) *9 — — — — — — — — — 100 No. 918(C)*10 2 2 2 2 2 2 — 2 2 2 Neostan U-300 (C1) *11 — — — — — — 2 — — —Aminosilane compound (D) *12 3 3 3 3 3 3 3 3 3 3 Vinyltrimethoxysilane 22 2 2 2 2 2 2 2 2 In Table 1, the amount of each of the materials to beblended is expressed in terms of part by weight, and the marks *1 to *12indicate the following: *1 the mixture 1 of crosslinkable silylgroup-containing polyoxyalkylene polymer (A: 150 parts by weight) andcrosslinkable silyl group-containing (meth)acrylic polymer (B: 100 partsby weight) obtained in Synthesis Example 1; *2 the mixture 2 ofcrosslinkable silyl group-containing polyox yalkylene polymer (A) andcrosslinkable silyl group-containing (meth)acrylic polymer (B) obtainedin Synthesis Example 2; *3 the mixture 3 of crosslinkable silylgroup-containing polyoxyalkylene polymer (A: 150 parts by weight) andcrosslinkable silyl group-containing (meth)acrylic polymer (B: 100 partsby weight) obtained in Synthesis Example 3; *4 the mixture 4 ofcrosslinkable silyl group-containing polyoxyalkylene polymer (A: 150parts by weight) and crosslinkable silyl group-containing (meth)acrylicpolymer (B: 100 parts by weight) obtained in Synthesis Example 4; *5 themixture 5 of crosslinkable silyl group-containing polyoxyalkylenepolymer (A: 150 parts by weight) and crosslinkable silylgroup-containing (meth)acrylic polymer (B: 100 parts by weight) obtainedin Synthesis Example 5; *6 the mixture 6 of crosslinkable silylgroup-containing polyoxyalkylene polymer (A: 150 parts by weight) andcrosslinkable silyl group-containing (meth)acrylic polymer (B: 100 partsby weight) obtained in Synthesis Example 6; *7 the crosslinkable silylgroup-containing (meth)acrylic polymer (B) obtained in ComparativeSynthesis Example 1; *8 the crosslinkable silyl group-containing(meth)acrylic polymer (B) obtained in Comparative Synthesis Example 2;*9 the crosslinkable silyl group-containing (meth)acrylic polymer (B)obtained in Comparative Synthesis Example 3; *10 reaction product ofdibutyltin oxide with phthalate manufactured by Sankyo Organic ChemicalsCo., Ltd. under the trade name of No. 918; *11 dibutyltin oxidemanufactured by Nitto Kasei Co., Ltd. under the trade name of NeostanU-300; and *12 N-β(aminoethyl)γ-aminopropyltrimethoxysilane.

Examples 2 to 6

In each of Examples 2 to 6, a curable composition was prepared, as inExample 1, by blending the materials shown in Table 1 in the blendingratio shown in Table 1.

Example 7

A curable composition was prepared in the same manner as in Example 1except that Neostan U-300 (dibutyltin oxide) was used in a predeterminedamount shown in Table 1 as the component (C) instead of No. 918 (that isa reaction product of dibutyltin oxide with phthalate). The resultantcurable composition was hermetically charged into a cartridge coatedwith aluminum, and was then subjected to heat curing at 50° C. for 3days. Thereafter, an experiment was conducted as in Example 1.

Comparative Examples 1 to 3

In each of Comparative Examples 1 to 3, a curable composition wasprepared, as in Example 1, by blending the materials shown in Table 1 inthe blending ratio shown in Table 1.

For each of these curable compositions obtained in Examples 1 to 7 andComparative Examples 1 to 3, the following measurements were carriedout, and measurement results are shown in Table 2.

1. Adhesion Properties

Adhesion properties were determined by a method for testing tensileshear strength of rigid adherebds in accordance with JIS K 6850. As theadherends, an alumite plate and a hemlock plate were used. Failureconditions were evaluated according to two criteria. Specifically, inTable 2, “∘” represents cohesive failure and “×” represents interfacialfailure.

2. Rubber-like Properties

Rubber-like properties were determined by a tensile testing method forvulcanized rubber in accordance with JIS K 6521 using a dumbbell-shapedtest piece No.3. In Table 2, “×” indicates that measurement wasimpossible.

3. Deep-part Curability

A container having a diameter of 4 cm or larger and a height of 2 cm orhigher and allowing moisture to pass through in only one direction wasfilled with the curable composition adjusted at 23° C., and then thesurface curable composition was leveled so as to be flat. The containerwas left under the conditions of 50% RH at 23° C. for 24 hours, and thenthe thickness of a cured portion was measured with a dial gauge.

4. Storage Stability

The viscosity of each of the curable compositions measured with a B-typeviscometer manufactured by Toki Sangyo Co., Ltd. (BS rotor No. 7; 10rpm) after being left under the conditions of 50% RH at 23° C. for 24hours was defined as an initial viscosity. Then, such a curablecomposition was further left in a drier at 50° C. for 2 weeks, and wasthen left under the conditions of 50% RH at 23° C. for 24 hours.Thereafter, the liquid temperature of the curable composition wasadjusted to 23° C. to again measure the viscosity thereof with the sameB-type viscometer as described above. The thus measured viscosity wasdefined as a viscosity after storage. The storage stability wasevaluated in terms of the value calculated from the formula: viscosityafter storage/initial viscosity. In Table 2, “∘” indicates that thevalue was less than 1.3, and “×” indicates that the value was 1.3 ormore.

5. Tack Free Drying Time

Tack free drying time was measured according to JIS A 1439 4.19. InTable 2, “∘” indicates that the tack free drying time was less than 10minutes, and “×” indicates that the tack free drying time was 10 minutesor longer.

TABLE 2 Comparative Examples Examples 1 2 3 4 5 6 7 1 2 3 Adhesion Finalstrength 3.1 2.7 2.1 2.1 2.2 2.7 3.2 2.6 2.4 1.6 properties (N/mm²)Failure conditions ◯ ◯ ◯ ◯ ◯ ◯ ◯ X X X Rubber-like Final strength 4.13.7 1.5 1.5 1.6 3.8 4.2 X X X properties (N/mm²) Elongation (%) 125 130110 110 120 90 130 X X X Deep-part curability (mm) 1.6 1.7 1.7 1.5 1.51.3 1.5 0.7 0.9 0.9 Storage stability ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Tack freedrying time ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯

As shown in Table 2, the curable compositions of Examples 1 to 7 wereexcellent in adhesion properties, rubber-like properties, deep-partcurability, and storage stability. On the other hand, the curablecompositions of Comparative Examples 1 to 3 which did not contain thecomponent (A) were poor in adhesion properties and rubber-likeproperties. In addition, the curable compositions of ComparativeExamples 1 to 3 were inferior in deep-part curability to the curablecompositions of Examples 1 to 7.

Example 8

The mixture 1 of a crosslinkable silyl group-containing polyoxyalkylenepolymer (A) and a crosslinkable silyl group-containing (meth)acrylicpolymer (B) obtained in Synthesis Example 1, a filler, andvinyltrimethoxysilane were blended in their respective predeterminedamounts shown in Table 3, and were then heated at 110° C. under areduced pressure while being stirred for 2 hours to remove water fromthe mixture. Further, an aminosilane compound and No. 918 (that is areaction product of dibutyltin oxide with phthalate) were added theretoin their respective predetermined amounts to prepare a curablecomposition.

TABLE 3 Comparative Example 8 Example 9 Example 4 Mixture 1 (A) + (B) *1100 — — Mixture 4 (A) + (B) *4 — 100 — Mixture 7 (A) *13 — — 100 No. 918(C) *10 2 2 2 Aminosilane compound 3 3 3 (D)*12 Filler *14 40 40 40Vinyltrimethoxysilane 2 2 2 In Table 3, the amount of each of thematerials to be blended is expressed in terms of part by weight, themarks *1, *4, *10 and *12 have the same meanings as described above withreference to Table 1, and the marks *13 and *14 indicate the following:*13 the mixture of crosslinkable silyl group-containing polyoxyalkylenepolymer (A: 150 parts by weight) and crosslinkable silylgroup-containing (meth)acrylic polymer (100 parts by weight) obtained inComparative Synthesis Example 4; and *14 calcium carbonate treated withfatty acid (manufactured by Maruo Calcium Co., Ltd. under the trade nameof “Calfine 200M”).

Example 9 and Comparative Example 4

In each of Example 9 and Comparative Example 4, a curable compositionwas prepared, as in Example 1, by blending the materials shown in Table3 in the blending ratio shown in Table 3.

For these curable compositions of Examples 8 and 9 and ComparativeExample 4, measurements were carried out to determine adhesionproperties, storage stability, and tack free drying time. Adhesionproperties were determined by a method for testing tensile shearstrength of rigid adherends in accordance with JIS K 6850 using variousadherends shown in Table 4. Storage stability and tack free drying timewere determined in the same manner as in Example 1. The measurementresults are shown in Table 4.

TABLE 4 Comparative Example 8 Example 9 Example 4 Adhesion Alumite 4.14.0 3.2 properties Acryl 4.0 4.1 3.0 Polycarbonate 4.1 4.1 3.1Polystyrene 2.9 2.8 2.5 ABS 3.5 3.7 2.8 Storage stability ◯ ◯ ◯ Tackfree drying time (min) <10 <10 15

As shown in Table 4, the curable compositions of Examples 8 and 9 wereexcellent in adhesion properties and adhesive strength. On the otherhand, the curable composition of Comparative Example 4 was inferior inadhesive strength to the curable compositions of Examples 8 and 9.

Synthesis Example 7

Polymerization of propylene oxide was carried out using glycerol as aninitiator and zinc hexacyanocobaltate as a catalyst to obtainpolyoxypropylenetriol. To the polyoxypropylenetriol,isocyanatepropyltrimethoxysilane was added to carry out a urethanizationreaction, to thereby obtain a trimethoxysilyl-terminated polymer P1having a molecular weight of 18,000.

Synthesis Example 8

Isocyanatepropyltrimethoxysilane was added to UH2000 manufactured byTOAGOSEI Co., Ltd. (molecular weight: 11,000; viscosity: 14,000mPa·S/25° C.; Tg: −55° C./DSC; OHV: 20 mg-KOH/g-resin) to carry out aurethanization reaction, to thereby obtain a trimethoxysilyl-terminatedpolymer P2.

Example 10

The crosslinkable silyl group-containing organic polymer (A), anantioxidant, calcium carbonate, and vinyltrimethoxysilane were blendedin their respective predetermined amounts shown in Table 5, and werethen heated at 110° C. under a reduced pressure while being stirred witha multi-purpose mixer (manufactured by Shinagawa Machinery Works Co.,Ltd.) for 2 hours to remove water from the mixture. Further, anaminosilane compound (D) and dibutyltin oxide (C1) were added thereto,and the mixture was stirred with a multi-purpose mixer (manufactured byShinagawa Machinery Works Co., Ltd.) under a reduced pressure for 10minutes to prepare a curable composition. The curable composition washermetically charged into an aluminum-coated cartridge.

TABLE 5 Comparative Examples Examples 10 11 12 13 14 5 6 Polymer P1 (A)*15 100 — 50 — 100 100 100 Polymer P2 (A) *16 — 100 — — — — — SAT-200(A) *17 — — 50 100 — — — STANN BO (C1) *18 2 2 2 2 — — — Neostan U-800 —— — — 3 — — (C1) *19 No. 918 (C) *10 — — — — — 4 — Neostan U-220 — — — —— — 4 (C) *20 Animosilane compound 2 2 2 2 2 2 2 (D) *12 Antioxidant *213 3 3 3 3 3 3 Filler *14 70 70 70 70 70 70 70 Vinyltrimethoxysilane 2 22 2 2 2 2 In Table 5, the amount of each of the materials to be blendedis expressed in terms of gram, the marks *10, *12, and *14 have the samemeaning as described above with reference to Tables 1 and 3, and themarks *15 to *21 indicate the following: *15 the polymer P1 produced inSynthesis Example 7; *16 the polymer P2 produced in Synthesis Example 8;*17 crosslinkable silyl group-containing polyoxyalkylene polymer(manufactured by KANEKA CORPORATION under the trade name of SAT-200 andhaving a difunctional crosslinkable silyl group); *18 dibutyltin oxide(manufactured by Sankyo Organic Chemicals Co., Ltd. under the trade nameof “STANN BO”); *19 dioctyltin oxide (manufactured by Nitto Kasei Co.,Ltd. under the trade name of “Neostan U-800”); *20 dibutyltindiacetylacetonate (manufactured by Nitto Kasei Co., Ltd. under the tradename of “Neostan U-220”); and *21 “Tinuvin B75” (trade name)manufactured by Ciba Specialty Chemicals Corp.

Examples 11 to 14 and Comparative Examples 5 and 6

In each of Examples 11 to 14 and Comparative Examples 5 and 6, a curablecomposition was prepared in the same manner as in Example 10 except thatthe materials to be blended and the blending ratio were changed as shownin Table 5.

The following performance tests were carried out on these curablecompositions of Examples 11 to 14 and Comparative Examples 5 and 6.

(1) Tack Free Drying Time

An experiment was carried out to check whether the tack free drying timeof each of the curable compositions of Example 10 and ComparativeExample 5 was changed by treatment at 20° C., 50° C. or 80° C. for apredetermined time after production. The tack free drying time wasmeasured according to JIS A 1439 4.19. The measurement results are shownin FIG. 1

As shown in FIG. 1, the tack free drying time of the curable compositionof Example 10 was changed according to the conditions of treatmentcarried out after production, such as temperature and elapsed time, butthe tack free drying time of the curable composition of ComparativeExample 5 was constant irrespective of the changes of temperature andelapsed time.

The tack free drying time of each of the curable compositions ofExamples 10 to 14 and Comparative Examples 5 and 6 was measured justafter production and after reaction treatment carried out under theconditions shown in Table 6. The measurement results are shown in Tables6 and 7 (Table 7 shows only the results measured after reactiontreatment was carried out).

TABLE 6 Comparative Examples Examples 10 11 12 13 14 5 6 Just afterproduction 480 460 720 1440 1200 5 5 (min) 20° C. 14 days 5 5 15 30 20 55 (min) 50° C. 3 days 5 5 15 30 20 5 5 (min) 80° C. 1 day 5 5 15 30 20 55 (min)(2) Production Stability

The production stability of the curable composition was evaluatedaccording to tack free drying time measured just after production. Theresults are shown in Table 7. In Table 7, “∘” indicates that the tackfree drying time was 30 minutes or longer, and “×” indicates that thetack free drying time was less than 30 minutes.

(3) Product Stability

The curable compositions of Examples 10 to 14 subjected to reactiontreatment at 50° C. for 3 days were prepared, and the curablecompositions of Comparative Examples 5 and 6 just after production wereprepared. The viscosity of each of such curable compositions measuredwith a B-type viscometer manufactured by Toki Sangyo Co., Ltd. (BS rotorNo. 7, 10 rpm) after being left under the conditions of 50% RH at 23° C.for 24 hours was defined as an initial viscosity. Then, such a curablecomposition was further left in a drier at 50° C. for 2 weeks, and wasthen left under the conditions of 50% RH at 23° C. for 24 hours.Thereafter, the liquid temperature of the curable composition wasadjusted to 23° C. to again measure the viscosity thereof with a B-typeviscometer manufactured by Toki Sangyo Co., Ltd. (BS rotor No. 7, 10rpm), and the viscosity was defined as a viscosity after storage. Thestorage stability was evaluated in terms of a value calculated from theformula: viscosity after storage/initial viscosity. The evaluationresults are shown in Table 7. In Table 7, “∘” indicates that the valuewas less than 1.3, and “×” indicates that the value was 1.3 or more.

(4) Adhesion Properties

The curable compositions of Examples 10 to 14 subjected to reactiontreatment at 50° C. for 3 days were prepared, and the curablecompositions of Comparative Examples 5 and 6 just after production wereprepared. Each of such curable compositions was applied onto an alumiteadherend in such a manner that the width, length, and height were 30 mm,50 mm, and 5 mm, respectively, and was then cured at 23° C. at 50% RHfor 14 days to prepare a test piece. After the completion of curing, anincision was made at the end portion of the test piece with a cutter,and then the curable composition was peeled off from the adherend withhands. The test results are shown in Table 7. In table 7, “∘” indicatescohesive failure and “×” indicates interfacial failure.

TABLE 7 Comparative Examples Examples 10 11 12 13 14 5 6 Productionstability ◯ ◯ ◯ ◯ ◯ X X Tack free drying time (min) 5 5 15 30 20 5 5Product stability ◯ ◯ ◯ ◯ ◯ X X Adhesion properties ◯ ◯ ◯ ◯ ◯ ◯ ◯

As shown in Tables 6 and 7, the curable compositions of Examples 10 and14 were excellent in production stability, quick curability, productstability and adhesion properties, but the curable compositions ofComparative Example 5 and 6 had problems in production stability andproduct stability.

INDUSTRIAL APPLICABILITY

The curable composition of the present invention may be used as aone-component curable composition or a two-component curable compositionif necessary, but is preferably used as a one-component curablecomposition. The curable composition of the present invention ispreferably used as, for example, sealants, adhesives, pressure-sensitiveadhesives, coating materials, and potting materials. Among them, thecurable composition of the present invention is particularly preferablyused as adhesives. In addition, the curable composition of the presentinvention can also be used for various purposes such as architecture,cars, civil engineering, and electrical and electronic fields.

1. A curable composition comprising: (A) a crosslinkable silylgroup-containing organic polymer, wherein the polymer (A) is at leastone selected from the group consisting of a crosslinkable silylgroup-containing polyoxyalkylene polymer, a crosslinkable silylgroup-containing (meth)acrylic-modified polyoxyalkylene polymer, acrosslinkable silyl group-containing polyisobutylene polymer, and acrosslinkable silyl group-containing (meth)acrylic polymer; and (C1) anorganotin compound represented by the following general formula (5):[Formula 5]R⁹R¹⁰SnO  (5) wherein R⁹ and R¹⁰ each represent a monovalent hydrocarbongroup, wherein a blending ratio of said organotin compound (C1) is 0.1to 30 parts by weight per 100 parts by weight of said crosslinkablesilyl group-containing organic polymer (A), wherein the curablecomposition is produced by a method comprising: providing a firstcurable composition including said crosslinkable silyl group-containingorganic polymer (A) and said organotin compound (C1) heating said firstcurable composition at 30 to 150° C. such that a curing speed of saidfirst curable composition is changed.
 2. A method for producing acurable composition, the method comprising: providing a first curablecomposition including (A) a crosslinkable silyl group-containing organicpolymer and (C1) an organotin compound represented by the followinggeneral formula (5): [Formula 5]R⁹R¹⁰SnO  (5) wherein R⁹ and R¹⁰ each represent a monovalent hydrocarbongroup, wherein a blending ratio of said organotin compound (C1) is 0.1to 30 parts by weight per 100 parts by weight of said crosslinkablesilyl group-containing organic polymer (A), wherein the polymer (A) isat least one selected from the group consisting of a crosslinkable silylgroup-containing polyoxyalkylene polymer, a crosslinkable silylgroup-containing (meth)acrylic-modified polyoxyalkylene polymer, acrosslinkable silyl group-containing polyisobutylene polymer, and acrosslinkable silyl group-containing (meth)acrylic polymer; heating saidfirst curable composition at 30 to 150° C. such that a cure speed ofsaid first curable composition is altered via said heating.
 3. Thecurable composition according to claim 1, wherein the polymer (A) is anorganic polymer containing a crosslinkable silyl group represented bythe following general formula (3): [Formula 3]—Si X₃   (3) wherein X represents a hydroxyl or hydrolyzable group, andthree Xs may be the same or different.
 4. The curable compositionaccording to claim 1, wherein the polymer (A) is an organic polymercontaining both of a crosslinkable silyl group represented by thefollowing general formula (3) and a crosslinkable silyl grouprepresented by the following general formula (4): [Formula 3]—Si X₃   (3) [Formula 4]

wherein X represents a hydroxyl or hydrolyzable group; when theplurality of Xs exist, they may be the same or different; R⁸ representsa substituted or unsubstituted monovalent organic group having 1 to 20carbon atoms; when the plurality of R⁸s exist, they may be the same ordifferent; and c is 1 or
 2. 5. The curable composition according toclaim 1, wherein the polymer (A) is a mixture of an organic polymercontaining a crosslinkable silyl group represented by the followinggeneral formula (3) and an organic polymer containing a crosslinkablesilyl group represented by the following general formula (4): [Formula3]—Si X₃   (3) [Formula 4]

wherein X represents a hydroxyl or hydrolyzable group; when theplurality of Xs exist, they may be the same or different; R⁸ representsa substituted or unsubstituted monovalent organic group having 1 to 20carbon atoms; when the plurality of R⁸s exist, they may be the same ordifferent; and c is 1 or
 2. 6. The curable composition according toclaim 1, further comprising a silane coupling agent (D), wherein ablending ratio of said silane coupling agent (D) is 0.1 to 30 parts byweight per 100 parts by weight of said crosslinkable silylgroup-containing organic polymer.
 7. The curable composition accordingto claim 1, further comprising (B) a (meth)acrylic polymer of which atleast one end is bonded to a residue, —S—R³ (where R³ represents a grouphaving a crosslinkable silyl group), wherein the residue is obtained byremoving a hydrogen atom from the crosslinkable silyl group-containingthiol compound, wherein the (meth)acrylic polymer is obtained bypolymerizing a (meth)acrylic monomer having a polymerizable unsaturatedbond in the presence of a metallocene compound represented by thefollowing formula (1) and the crosslinkable silyl group-containing thiolcompound, and wherein said metallocene compound and said crosslinkablesilyl group-containing thiol compound are used in a mole ratio of 100:1to 1:50,000: [Formula 1]

wherein M represents a metal selected from the group consisting ofmetals of Groups 4, 5, and 14 of the periodic table, chromium,ruthenium, and palladium; R¹ and R² each independently represent atleast one group selected from the group consisting of substituted orunsubstituted aliphatic hydrocarbon groups, substituted or unsubstitutedalicyclic hydrocarbon groups, substituted or unsubstituted aromatichydrocarbon groups, and substituted or unsubstituted silicon-containinggroups, a hydrogen atom or a single bond, R¹ and R² may cooperate witheach other to bond the two five-membered rings of the compoundrepresented by the formula (1) and the plurality of adjacent groups R¹or R² may cooperate with each other to form a cyclic structure; a and beach independently represent an integer of 1 to 4; Y represents ahalogen atom or a hydrocarbon group in which at least part of hydrogenatoms may be substituted with a halogen atom; and n is 0 or an integerobtained by subtracting 2 from the valence of the metal M, wherein ablending ratio of said (meth)acrylic polymer (B) is 0.01 to 100 parts byweight per one part by weight of said crosslinkable silylgroup-containing organic polymer (A).
 8. The method according to claim2, wherein the first curable composition comprises (B) a (meth)acrylicpolymer of which at least one end is bonded to a residue, —S—R³ (whereR³ represents a group having a crosslinkable silyl group), wherein theresidue is obtained by removing a hydrogen atom from the crosslinkablesilyl group-containing thiol compound, wherein the (meth)acrylic polymeris obtained by polymerizing a (meth)acrylic monomer having apolymerizable unsaturated bond in the presence of a metallocene compoundrepresented by the following formula (1) and the crosslinkable silylgroup-containing thiol compound, and wherein said metallocene compoundand said crosslinkable silyl group-containing thiol compound are used ina mole ratio of 100:1 to 1:50,000: [Formula 1]

wherein M represents a metal selected from the group consisting ofmetals of Groups 4, 5, and 14 of the periodic table, chromium,ruthenium, and palladium; R¹ and R² each independently represent atleast one group selected from the group consisting of substituted orunsubstituted aliphatic hydrocarbon groups, substituted or unsubstitutedalicyclic hydrocarbon groups, substituted or unsubstituted aromatichydrocarbon groups, and substituted or unsubstituted silicon-containinggroups, a hydrogen atom or a single bond, R¹ and R² may cooperate witheach other to bond the two five-membered rings of the compoundrepresented by the formula (1) and the plurality of adjacent groups R¹or R² may cooperate with each other to form a cyclic structure; a and beach independently represent an integer of 1 to 4; Y represents ahalogen atom or a hydrocarbon group in which at least part of hydrogenatoms may be substituted with a halogen atom; and n is 0 or an integerobtained by subtracting 2 from the valence of the metal M, wherein ablending ratio of said (meth)acrylic polymer (B) is 0.01 to 100 parts byweight per one part by weight of said crosslinkable silylgroup-containing organic polymer (A).
 9. The curable compositionaccording to claim 1, wherein said first curable composition is heatedin a hermetically sealed container at 30 to 150° C.
 10. The methodaccording to claim 2, wherein said first curable composition is heatedin a hermetically sealed container at 30 to 150° C.
 11. The methodaccording to claim 2, wherein the polymer (A) is an organic polymercontaining a crosslinkable silyl group represented by the followinggeneral formula [Formula 3]—Si X₃   (3) wherein X represents a hydroxyl or hydrolyzable group, andthree Xs may be the same or different.
 12. The method according to claim2, wherein the polymer (A) is an organic polymer containing both of acrosslinkable silyl group represented by the following general formula(3) and a crosslinkable silyl group represented by the following generalformula (4): [Formula 3]—Si X₃   (3) [Formula 4]

wherein X represents a hydroxyl or hydrolyzable group; when theplurality of Xs exist, they may be the same or different; R⁸ representsa substituted or unsubstituted monovalent organic group having 1 to 20carbon atoms; when the plurality of R⁸ exist, they may be the same ordifferent; and c is 1 or
 2. 13. The method according to claim 2, whereinthe polymer (A) is a mixture of an organic polymer containing acrosslinkable silyl group represented by the following general formula(3) and an organic polymer containing a crosslinkable silyl grouprepresented by the following general formula (4): [Formula 3]—Si X₃  (3) [Formula 4]

wherein X represents a hydroxyl or hydrolyzable group; when theplurality of Xs exist, they may be the same or different; R⁸ representsa substituted or unsubstituted monovalent organic group having 1 to 20carbon atoms; when the plurality of R⁸s exist, they may be the same ordifferent; and c is 1 or
 2. 14. The method according to claim 2, whereinthe first curable composition further comprises a silane coupling agent(D), wherein a blending ratio of said silane coupling agent (D) is 0.1to 30 parts by weight per 100 parts by weight of said crosslinkablesilyl group-containing organic polymer.